CHAPTER 18 . Metals Analysis by High Performance Liquid Chromatography
353
EDTA-oxalic acid} has been optimized by working at a 40°C column temperature
(Inoue et al. 1995). Detection was obtained by direct introduction of an eluate into an
ICP-MS system. This method enabled 80-88 ng rl detection limits for Cr(III} and
Cr(VI) respectively within a linear range from 0.5 to 5000 flg Cr rl and simultaneous
determination of chromium species and Mn, Fe, Ni, Cu, Mg and Ca in water samples.
Total chromium, Cr(III) and Cr(VI) speciation was achieved (Powell et al. 1995) by
coupling HPL anion-chromatography (eluent nitric acid) with direct injection nebulization and ICP-MS. The detection limits obtained were 30 and 60 ng rl for Cr(III}
and Cr(VI) respectively without particular chromatographic approach. Mixed-mode
columns were used (Byrdy et al.1995), namely IonPac AS7, for Cr(III} and Cr(VI) separation with (NH4hS04 eluent (pH 9.2). Cr(III) species was stabilized with EDTA before sample analysis and detection was performed both by ICP-AES and ICP-MS
equipped with a high-performance interface and a concentric nebulizer. Relative detection limits were 0.40 ng rl for Cr(III} and 1.0 flg rl for Cr(VI} within a 4% RSD
and a linear dinamic range from 3 to 600 flg rl and from 5 to 1000 flg rl for Cr(III)
and Cr(VI) respectively in aqueous media.
At the end of these examples it seems a matter of philosophy to define LC a separation technique coupled with a specific detector or a tool for on-line sample pretreatments (Buchberger and Haddad 1997).
References
Abollino 0, Mentasti E, Porta V, Sarzanini C (1990) Immobilized 8-oxine units on different solid
sorbents for the uptake of metal traces. Anal Chern 62:21-26
Abollino 0, Sarzanini C, Mentasti E, Liberatori A (1993) Trace metal pre-concentration with sulfonated
azo-dyes and ICP AES determination. Spectrochim Acta 49A:1411-1421
Alvarez-Zepeda A, Barman BN, Martire DE (1992) Thermodynamic study of the marked differences
between acetonitrile - water and methanol - water mobile phase systems in reversed-phase liquid chromatography. Anal Chern 64:1978-1984
Branch S, Corns WT, Ebdon L, Hill S, O'Neil P (1991) Determination of arsenic by hydride-generation
inductively-coupled plasma mass spectrometry using a tubular membrane gas - liquid separator.
J Anal At Spectrom 6:155-158
Braverman DS (1992) Determination of rare-earth elements [in fly ash] by liquid-chromatographic separation using inductively-coupled plasma mass spectrometric detection. J Anal At Spectrom 7:43-46
Buchberger W, Haddad PR (1997) Advances in detection techniques for ion chromatography. J
Chromatogr A 789:67-83
Byrdy FA, Olson LK, Vela NP, Caruso JA (1995) Chromium speciation by anion-exchange high-performance liquid chromatography with both inductively-coupled plasma atomic-emission
spectroscopic and inductively-coupled plasma mass spectrometric detection. J Chromatogr
712:311-320
Caprioli R, Torcini S (1993) Determination of copper, nickel, zinc, cobalt and manganese in sea-water
by chelation ion chromatography. J Chromatogr 640:365-369
Cardellicchio N, Cavalli S, Riviello JM (1993) Determination of cadmium and lead at I1grllevels in
aqueous matrices by chelation ion chromatography. J Chromatogr 640:207-216
Cardellicchio N, Ragone P, Cavalli S, Riviello J (1997) Use of ion chromatography for the determination of transition metals in the control of sewage-treatment-plant and related waters. J Chromatogr
A 770:185-193
Cassidy RM, Sun L (1993) Optimization of the anion-exchange separation of metal-oxalate complexes.
J Chromatogr 654:105-111
Challenger OJ, Hill SJ, Jones P, Barnett NW (1992) Application of chelating exchange ion chromatography to the determination of trace metals in high ionic strength media. Anal Proc 29:91-93
Challenger OJ, Hill SJ, Jones P (1993) Separation and determination of trace metals in concentrated
salt solutions using chelation ion chromatography. J Chromatogr 639:197-205
Comber S (1993) Determination of dissolved copper, nickel and cadmium in natural waters by highperformance liquid chromatography. Analyst 118:505-509
353
EDTA-oxalic acid} has been optimized by working at a 40°C column temperature
(Inoue et al. 1995). Detection was obtained by direct introduction of an eluate into an
ICP-MS system. This method enabled 80-88 ng rl detection limits for Cr(III} and
Cr(VI) respectively within a linear range from 0.5 to 5000 flg Cr rl and simultaneous
determination of chromium species and Mn, Fe, Ni, Cu, Mg and Ca in water samples.
Total chromium, Cr(III) and Cr(VI) speciation was achieved (Powell et al. 1995) by
coupling HPL anion-chromatography (eluent nitric acid) with direct injection nebulization and ICP-MS. The detection limits obtained were 30 and 60 ng rl for Cr(III}
and Cr(VI) respectively without particular chromatographic approach. Mixed-mode
columns were used (Byrdy et al.1995), namely IonPac AS7, for Cr(III} and Cr(VI) separation with (NH4hS04 eluent (pH 9.2). Cr(III) species was stabilized with EDTA before sample analysis and detection was performed both by ICP-AES and ICP-MS
equipped with a high-performance interface and a concentric nebulizer. Relative detection limits were 0.40 ng rl for Cr(III} and 1.0 flg rl for Cr(VI} within a 4% RSD
and a linear dinamic range from 3 to 600 flg rl and from 5 to 1000 flg rl for Cr(III)
and Cr(VI) respectively in aqueous media.
At the end of these examples it seems a matter of philosophy to define LC a separation technique coupled with a specific detector or a tool for on-line sample pretreatments (Buchberger and Haddad 1997).
References
Abollino 0, Mentasti E, Porta V, Sarzanini C (1990) Immobilized 8-oxine units on different solid
sorbents for the uptake of metal traces. Anal Chern 62:21-26
Abollino 0, Sarzanini C, Mentasti E, Liberatori A (1993) Trace metal pre-concentration with sulfonated
azo-dyes and ICP AES determination. Spectrochim Acta 49A:1411-1421
Alvarez-Zepeda A, Barman BN, Martire DE (1992) Thermodynamic study of the marked differences
between acetonitrile - water and methanol - water mobile phase systems in reversed-phase liquid chromatography. Anal Chern 64:1978-1984
Branch S, Corns WT, Ebdon L, Hill S, O'Neil P (1991) Determination of arsenic by hydride-generation
inductively-coupled plasma mass spectrometry using a tubular membrane gas - liquid separator.
J Anal At Spectrom 6:155-158
Braverman DS (1992) Determination of rare-earth elements [in fly ash] by liquid-chromatographic separation using inductively-coupled plasma mass spectrometric detection. J Anal At Spectrom 7:43-46
Buchberger W, Haddad PR (1997) Advances in detection techniques for ion chromatography. J
Chromatogr A 789:67-83
Byrdy FA, Olson LK, Vela NP, Caruso JA (1995) Chromium speciation by anion-exchange high-performance liquid chromatography with both inductively-coupled plasma atomic-emission
spectroscopic and inductively-coupled plasma mass spectrometric detection. J Chromatogr
712:311-320
Caprioli R, Torcini S (1993) Determination of copper, nickel, zinc, cobalt and manganese in sea-water
by chelation ion chromatography. J Chromatogr 640:365-369
Cardellicchio N, Cavalli S, Riviello JM (1993) Determination of cadmium and lead at I1grllevels in
aqueous matrices by chelation ion chromatography. J Chromatogr 640:207-216
Cardellicchio N, Ragone P, Cavalli S, Riviello J (1997) Use of ion chromatography for the determination of transition metals in the control of sewage-treatment-plant and related waters. J Chromatogr
A 770:185-193
Cassidy RM, Sun L (1993) Optimization of the anion-exchange separation of metal-oxalate complexes.
J Chromatogr 654:105-111
Challenger OJ, Hill SJ, Jones P, Barnett NW (1992) Application of chelating exchange ion chromatography to the determination of trace metals in high ionic strength media. Anal Proc 29:91-93
Challenger OJ, Hill SJ, Jones P (1993) Separation and determination of trace metals in concentrated
salt solutions using chelation ion chromatography. J Chromatogr 639:197-205
Comber S (1993) Determination of dissolved copper, nickel and cadmium in natural waters by highperformance liquid chromatography. Analyst 118:505-509